EP2697297B1 - Moulding material for cushions - Google Patents

Moulding material for cushions Download PDF

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Publication number
EP2697297B1
EP2697297B1 EP11725958.0A EP11725958A EP2697297B1 EP 2697297 B1 EP2697297 B1 EP 2697297B1 EP 11725958 A EP11725958 A EP 11725958A EP 2697297 B1 EP2697297 B1 EP 2697297B1
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EP
European Patent Office
Prior art keywords
fibres
impact
expanded
spheres
hollow
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP11725958.0A
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German (de)
French (fr)
Other versions
EP2697297A1 (en
Inventor
Andrea DEL GUASTA
Giuseppe PARONETTO
Andrea Antichi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tryonic Ltd
Original Assignee
Tryonic Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tryonic Ltd filed Critical Tryonic Ltd
Publication of EP2697297A1 publication Critical patent/EP2697297A1/en
Application granted granted Critical
Publication of EP2697297B1 publication Critical patent/EP2697297B1/en
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Classifications

    • A—HUMAN NECESSITIES
    • A42—HEADWEAR
    • A42B—HATS; HEAD COVERINGS
    • A42B3/00—Helmets; Helmet covers ; Other protective head coverings
    • A42B3/04—Parts, details or accessories of helmets
    • A42B3/10—Linings
    • A42B3/12—Cushioning devices
    • A42B3/125—Cushioning devices with a padded structure, e.g. foam
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/14—Soles; Sole-and-heel integral units characterised by the constructive form
    • A43B13/18—Resilient soles
    • A43B13/187—Resiliency achieved by the features of the material, e.g. foam, non liquid materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/02—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising combinations of reinforcements, e.g. non-specified reinforcements, fibrous reinforcing inserts and fillers, e.g. particulate fillers, incorporated in matrix material, forming one or more layers and with or without non-reinforced or non-filled layers
    • B29C70/021—Combinations of fibrous reinforcement and non-fibrous material
    • B29C70/025—Combinations of fibrous reinforcement and non-fibrous material with particular filler
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0085—Use of fibrous compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/232—Forming foamed products by sintering expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/236—Forming foamed products using binding agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B29K2105/046—Condition, form or state of moulded material or of the material to be shaped cellular or porous with closed cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B29K2105/165—Hollow fillers, e.g. microballoons or expanded particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/48—Wearing apparel
    • B29L2031/4807—Headwear
    • B29L2031/4814—Hats
    • B29L2031/4821—Helmets

Definitions

  • the invention relates to a protective padding cap of a helmet, according to claim 1.
  • the most commonly used material for making high impact padding such as the internal protection of helmets, is expanded polystyrene (EPS).
  • EPS expanded polystyrene
  • WO 96/05240 refers to means for improving the strength of hollow mechanical structures, and especially for improving the impact strength of structural members in motor vehicles.
  • the invention is a method of strengthening a portion of a hollow member, by inserting into the hollow member a precursor mixture comprising the combination of both components of a 2-part resin mix, where such combination alone would have a specific gravity between 1.05 and 1.25, and hollow micro-spheres having a shell of material different to that of said resin mix.
  • WO 99/44813 discloses a cellular material, comprising expanded micro-spheres of a polymeric gas-tight shell, to make protection equipments, such as helmets.
  • US 4 252 910 discloses a material for use in resilient conforming pads, cushions and the like.
  • the material comprises elastic gas-filled hollow micro-particles cohered to a mass by a thermoplastic bonding agent semi-liquid at body temperature.
  • the main object is to provide a different material, preferably with the ability to absorb impact with an energy-dispersion elastic response and no structural collapse, so as to have a material reactive to multiple impacts.
  • the preferred basic formula of the raw material in other words before heating in the mould, is 20-50% in weight of expanded particles (microspheres) and 80-50% in weight of non-expanded particles (microspheres). Such values ensure advantageous performances and weights and suitable for the applications, in particular excellent impact absorption results and lightness.
  • the non-expanded microspheres or spheres are in plastic material, and are closed spheres. They are hollow and full of gas which expands when heated making the sphere dilate and reducing the overall density of the material. It should be said that the apparent density does not change (the mould is filled completely) but the real density does, because the air between the spheres is expelled.
  • the expanded particles are essential for the invention.
  • the expanded microspheres are in plastic material, in particular in thermoplastic acrylic resin. They are closed spheres, hollow and full of gas; and act as a binding agent or filler for the other spheres. In fact the expanded spheres are the filler element, the non-expanded ones acting as a binding agent.
  • the non-expanded particles are combined with another binding material or component which is a glue and/or viscose glue such as polyurethane, in which case however the production system would need to be accordingly modified and performance could vary.
  • the non-expanded particles are a material which expands with heat, but a cold-setting material may be used such as a dual component glue, or polyurethane, or one which expands with a catalyst, such as polyurethane.
  • microspheres It is important for the microspheres to be:
  • Spheres which can be used for the invention are for example contained in the material Expancell®.
  • the particles are generally of spherical shape and are very small (10-40 ⁇ m diameter). Note however that such dimensions are not essential.
  • the material gives the moulded product a shape memory.
  • the expanded and non-expanded spheres compress or dilate in its mass. Thanks to the elasticity of the spheres, when the stress ceases each sphere returns to its original state, and consequently the material resumes its original form.
  • the moulded product reacts to a second deformation in the same way as to the first, with obvious advantages for safety and repeatability of the reaction to impact.
  • anti-sedimenting components may also be used, except for example waxes, silicones or Teflon which reduce the adhesion of the particles excessively.
  • the purpose of the anti-sedimenting agent is to improve the flow/insertion of the composite material inside the mould.
  • hydrophobic type If an anti-sedimenting component such as silica is used, there being two types (hydrophilic and hydrophobic) the hydrophobic type must be chosen.
  • the fibres are used to make the material tougher like all fibres in composites.
  • Polyethylene fibres (PE) for example are preferred, it being possible to replace them with any fibre (carbon, Kevlar, glass etc). It is sufficient for there to be a bond between the material and the fibres.
  • the material has the advantage of surviving stress through various impact cycles, given that its cells are completely closed so that nothing can collapse during stress.
  • the best density: elasticity ratio is achieved with a specific weight of 30-40kg/m 3 . This density guarantees moreover excellent filling of the mould, improved conductivity and a complete and even firing of the object.
  • the material solidifies after being heated in the mould.
  • the expansion temperature of the material in the mould is 100-160 °C. Over such temperature there is a risk of breakdown, invalidating impact absorption performance.
  • Another advantage of the material is that it has a lower density than EPS. Lighter objects of the same volume can be made, or with higher absorption capacities for the same volume.
  • the material has proved to be easy to process, thereby enabling a limitation of industrial costs
  • test results were compared with a cap produced with the EPS normally used.
  • the points of impact were: left forehead, left temple, the back at the edge of the impact area, right temple, right forehead.
  • G is the deceleration value (negative g) which the protective device applies to the wearer's head, namely decelerating by a certain speed (established by law) up to complete standstill.
  • the HIC (Head Injury Criterion) value represents the maximum value achievable below a standard deceleration curve, where the x-axis is the time of impact in milliseconds and the y-axis is the deceleration: it is the time interval calculated in which the area peak occurs.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Helmets And Other Head Coverings (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

  • The invention relates to a protective padding cap of a helmet, according to claim 1. The most commonly used material for making high impact padding, such as the internal protection of helmets, is expanded polystyrene (EPS). Despite its diffusion it has disadvantages which have stimulated the search for other improved materials. In particular, polystyrene
    • absorbs impact through the irreversible collapse of its structure (partially closed cell, in other words containing a collapsible alveolar structure), thus being effective for one impact only, the first;
    • it is sensitive to high temperatures, and in extreme applications such as competitions in the desert (over 60°C) may modify its state and become soft;
    • it has a non-negligible density.
  • WO 96/05240 refers to means for improving the strength of hollow mechanical structures, and especially for improving the impact strength of structural members in motor vehicles. The invention is a method of strengthening a portion of a hollow member, by inserting into the hollow member a precursor mixture comprising the combination of both components of a 2-part resin mix, where such combination alone would have a specific gravity between 1.05 and 1.25, and hollow micro-spheres having a shell of material different to that of said resin mix.
  • WO 99/44813 discloses a cellular material, comprising expanded micro-spheres of a polymeric gas-tight shell, to make protection equipments, such as helmets.
  • US 4 252 910 discloses a material for use in resilient conforming pads, cushions and the like. The material comprises elastic gas-filled hollow micro-particles cohered to a mass by a thermoplastic bonding agent semi-liquid at body temperature.
  • The main object is to provide a different material, preferably with the ability to absorb impact with an energy-dispersion elastic response and no structural collapse, so as to have a material reactive to multiple impacts.
  • The preferred basic formula of the raw material, in other words before heating in the mould, is 20-50% in weight of expanded particles (microspheres) and 80-50% in weight of non-expanded particles (microspheres). Such values ensure advantageous performances and weights and suitable for the applications, in particular excellent impact absorption results and lightness.
  • With the heat of the mould, where the compound hardens, all the microspheres expand (though the expanded ones less).
  • The non-expanded microspheres or spheres are in plastic material, and are closed spheres. They are hollow and full of gas which expands when heated making the sphere dilate and reducing the overall density of the material. It should be said that the apparent density does not change (the mould is filled completely) but the real density does, because the air between the spheres is expelled.
  • The expanded particles are essential for the invention. The expanded microspheres are in plastic material, in particular in thermoplastic acrylic resin. They are closed spheres, hollow and full of gas; and act as a binding agent or filler for the other spheres. In fact the expanded spheres are the filler element, the non-expanded ones acting as a binding agent.
  • The non-expanded particles are combined with another binding material or component which is a glue and/or viscose glue such as polyurethane, in which case however the production system would need to be accordingly modified and performance could vary. The non-expanded particles are a material which expands with heat, but a cold-setting material may be used such as a dual component glue, or polyurethane, or one which expands with a catalyst, such as polyurethane.
  • It is important for the microspheres to be:
    • closed spheres, since the closed structure enables them to absorb and disperse energy;
    • low in density and therefore lightweight;
    • viscoelastic: if they were only viscose they would not return to position making the material multi-impact, while if they were only elastic they would not absorb energy;
    • able to stick to each other so as to create a compact material.
  • The implicit lightness of the aforesaid materials is not necessary but extremely advantageous in the finished product.
  • Spheres which can be used for the invention are for example contained in the material Expancell®.
  • The particles are generally of spherical shape and are very small (10-40 µm diameter). Note however that such dimensions are not essential.
  • One advantage of the material is that it gives the moulded product a shape memory. When the product undergoes deformation, the expanded and non-expanded spheres compress or dilate in its mass. Thanks to the elasticity of the spheres, when the stress ceases each sphere returns to its original state, and consequently the material resumes its original form. Note too that the moulded product reacts to a second deformation in the same way as to the first, with obvious advantages for safety and repeatability of the reaction to impact.
  • The following is added to the basic formula as above:
    • 0-2% of pyrogenic silica, for example of the Aerosil® type, to prevent the formation of lumps, facilitate flow during insertion in the mould and partially reduce the entrance of water. In general, any component reducing the entrance of water may be used, and a water-repellent component is not necessary. In fact the silica does not make the material water-repellent; but having a water-repellent material helps for example in helmet applications.
  • The following may be optionally added to the basic formula as above:
    • about 0-3% of fibres in polyethylene or material which does not make the product absorb water, or which above all makes it tougher. The fibres are not used to make the material water-repellent but tougher.
  • With the silica, functionally similar anti-sedimenting components may also be used, except for example waxes, silicones or Teflon which reduce the adhesion of the particles excessively. The purpose of the anti-sedimenting agent is to improve the flow/insertion of the composite material inside the mould.
  • If an anti-sedimenting component such as silica is used, there being two types (hydrophilic and hydrophobic) the hydrophobic type must be chosen.
  • The fibres, or analogous component, are used to make the material tougher like all fibres in composites. Polyethylene fibres (PE) for example are preferred, it being possible to replace them with any fibre (carbon, Kevlar, glass etc). It is sufficient for there to be a bond between the material and the fibres.
  • The material has the advantage of surviving stress through various impact cycles, given that its cells are completely closed so that nothing can collapse during stress.
  • The best density: elasticity ratio is achieved with a specific weight of 30-40kg/m3. This density guarantees moreover excellent filling of the mould, improved conductivity and a complete and even firing of the object.
  • As mentioned, the material solidifies after being heated in the mould.
    The expansion temperature of the material in the mould is 100-160 °C. Over such temperature there is a risk of breakdown, invalidating impact absorption performance.
  • Another advantage of the material is that it has a lower density than EPS. Lighter objects of the same volume can be made, or with higher absorption capacities for the same volume.
  • Moreover, the material has proved to be easy to process, thereby enabling a limitation of industrial costs
  • Experimental protective caps were made for the inside of motorbike helmets in an aluminium mould and then tested by means of artificial impact.
  • The test results were compared with a cap produced with the EPS normally used.
  • The points of impact, the same for all the helmets tested, were: left forehead, left temple, the back at the edge of the impact area, right temple, right forehead.
  • Three impacts were performed on each point:
    1. 1. first impact with energy of over 150J (SNELL SA2005),
    2. 2. second impact with energy of over 110J (SNELL SA2005),
    3. 3. third impact with energy over 110J (further impact for experimental purposes only).
  • Compared to standard EPS, G and HIC values of up to one-third less were achieved.
  • G is the deceleration value (negative g) which the protective device applies to the wearer's head, namely decelerating by a certain speed (established by law) up to complete standstill. The HIC (Head Injury Criterion) value represents the maximum value achievable below a standard deceleration curve, where the x-axis is the time of impact in milliseconds and the y-axis is the deceleration: it is the time interval calculated in which the area peak occurs.

Claims (4)

  1. Protective padding cap of a helmet
    made of a raw material solidified after being heated in a mould,
    the material before heating being composed in weight of 20-50% of expanded particles and 80-50% of binding component,
    the particles being made of plastic material, of closed shape, hollow and filled with gas,
    wherein the binding component comprises
    (i) non-expanded particles, in plastic material, of closed shape, hollow and filled with gas, characterized by the fact that the binding component further comprises
    (ii) a glue,
    and in that the raw material comprises 0-2% in weight of pyrogenic silica.
  2. Cap according to claim 1, wherein the material comprises 0-3% in weight of fibres.
  3. Cap according to claim 2, wherein the fibres comprise fibres in polyethylene.
  4. Cap according to claim 2, wherein the fibres comprise carbon, Kevlar or glass fibres.
EP11725958.0A 2011-04-13 2011-04-13 Moulding material for cushions Active EP2697297B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IB2011/051598 WO2012140473A1 (en) 2011-04-13 2011-04-13 Moulding material for cushions

Publications (2)

Publication Number Publication Date
EP2697297A1 EP2697297A1 (en) 2014-02-19
EP2697297B1 true EP2697297B1 (en) 2017-05-24

Family

ID=44514840

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11725958.0A Active EP2697297B1 (en) 2011-04-13 2011-04-13 Moulding material for cushions

Country Status (4)

Country Link
US (1) US20140033401A1 (en)
EP (1) EP2697297B1 (en)
CN (1) CN103517939A (en)
WO (1) WO2012140473A1 (en)

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GB201603566D0 (en) * 2016-03-01 2016-04-13 Mips Ab Helmet
ITUA20161692A1 (en) * 2016-03-15 2017-09-15 Tryonic Ltd "Method to stabilize the size of a printed object"
WO2018027187A1 (en) * 2016-08-05 2018-02-08 Amtek Research International Llc Solidified, conformable porous composites and related devices, methods, and uses
US11374227B2 (en) 2018-02-02 2022-06-28 Amtek Research International Llc Dry process electrically conductive composite formation
IT201900013098A1 (en) 2019-07-26 2021-01-26 Giorgia Daniel "Composite material for hot forging"
IT201900014454A1 (en) 2019-08-08 2021-02-08 Daniel Giorgia "Composite material and hot stamping method"
CN114098208A (en) * 2021-12-22 2022-03-01 乐清市智能装备与制造研究院 Bulletproof helmet and manufacturing method of bulletproof helmet based on 3D printing technology

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Publication number Priority date Publication date Assignee Title
US4252910A (en) * 1973-07-16 1981-02-24 Philipp Schaefer Material for resilient, conforming pads, cushions, supports or the like and method
EP0585965A1 (en) * 1989-07-12 1994-03-09 Teijin Limited Process for the production of composite molded articles
EP0893332A1 (en) * 1997-07-21 1999-01-27 Henkel Corporation Method for reinforcing structural members
WO1999044813A1 (en) * 1998-03-04 1999-09-10 Ruden Aake Utilization of expanded microspheres as shock absorbing material in safety devices

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SE8100819L (en) * 1981-02-05 1982-08-06 Kema Nord Ab HEART IMPROVED FIBER COMPOSITION MATERIAL
US4595623A (en) * 1984-05-07 1986-06-17 Hughes Aircraft Company Fiber-reinforced syntactic foam composites and method of forming same
EP0380523A1 (en) * 1987-08-03 1990-08-08 AlliedSignal Inc. Impact resistant helmet
AUPM739694A0 (en) * 1994-08-11 1994-09-01 Russell, Terence Alan Structural strengthening
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Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4252910A (en) * 1973-07-16 1981-02-24 Philipp Schaefer Material for resilient, conforming pads, cushions, supports or the like and method
EP0585965A1 (en) * 1989-07-12 1994-03-09 Teijin Limited Process for the production of composite molded articles
EP0893332A1 (en) * 1997-07-21 1999-01-27 Henkel Corporation Method for reinforcing structural members
WO1999044813A1 (en) * 1998-03-04 1999-09-10 Ruden Aake Utilization of expanded microspheres as shock absorbing material in safety devices

Also Published As

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US20140033401A1 (en) 2014-02-06
CN103517939A (en) 2014-01-15
EP2697297A1 (en) 2014-02-19
WO2012140473A1 (en) 2012-10-18

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